Magnetic trapping of Yb in the metastable P-3(2) state

We report magnetic trapping of Yb in the excited P-3(2) state. This state, with a lifetime of 15 s, could play an important role in studies ranging from optical clocks and quantum computation to the search for a permanent electric dipole moment. Yb atoms are first cooled and trapped in the ground state in a 399-nm magneto-optic trap. The cold atoms are then pumped into the excited state by driving the S-1(0) -> P-3(1) -> S-3(1) transition. Atoms in the P-3(2) state are magnetically trapped in a spherical quadrupole field with an axial gradient of 110 G/cm. We trap up to 10(6) atoms with a lifetime of 1.5 s.

Precise measurement of hyperfine structure in the 2P(1/2) state of Li-7 using saturated-absorption spectroscopy

We report a precise measurement of the hyperfine interval in the 2P(1/2) state of Li-7. The transition from the ground state (D-1 line) is accessed using a diode laser and the technique of saturated-absorption spectroscopy in hot Li vapor. The interval is measured by locking an acousto-optic modulator to the frequency difference between the two hyperfine peaks. The measured interval of 92.040(6) MHz is consistent with an earlier measurement reported by us using an atomic-beam spectrometer Das and Natarajan, J. Phys. B 41, 035001 (2008)]. The interval yields the magnetic dipole constant in the P-1/2 state as A = 46.047(3), which is discrepant from theoretical calculations by > 80 kHz.

Denumerable state stochastic games with limiting average payoff

We study stochastic games with countable state space, compact action spaces, and limiting average payoff. ForN-person games, the existence of an equilibrium in stationary strategies is established under a certain Liapunov stability condition. For two-person zero-sum games, the existence of a value and optimal strategies for both players are established under the same stability condition.

Spin state and exchange in the quasi-one-dimensional antiferromagnet KFeS2

We report the optical spectra and single crystal magnetic susceptibility of the one-dimensional antiferromagnet KFeS2. Measurements have been carried out to ascertain the spin state of Fe3+ and the nature of the magnetic interactions in this compound. The optical spectra and magnetic susceptibility could be consistently interpreted using a S = 1/2 spin ground state for the Fe3+ ion. The features in the optical spectra have been assigned to transitions within the d-electron manifold of the Fe3+ ion, and analysed in the strong field limit of the ligand field theory. The high temperature isotropic magnetic susceptibility is typical of a low-dimensional system and exhibits a broad maximum at similar to 565 K. The susceptibility shows a well defined transition to a three dimensionally ordered antiferromagnetic state at T-N = 250 K. The intra and interchain exchange constants, J and J', have been evaluated from the experimental susceptibilities using the relationship between these quantities, and chi(max), T-max, and T-N for a spin 1/2 one-dimensional chain. The values are J = -440.71 K, and J' = 53.94 K. Using these values of J and J', the susceptibility of a spin 1/2 Heisenberg chain was calculated. A non-interacting spin wave model was used below T-N. The susceptibility in the paramagnetic region was calculated from the theoretical curves for an infinite S = 1/2 chain. The calculated susceptibility compares well with the experimental data of KFeS2. Further support for a one-dimensional spin 1/2 model comes from the fact that the calculated perpendicular susceptibility at 0K (2.75 x 10(-4) emu/mol) evaluated considering the zero point reduction in magnetization from spin wave theory is close to the projected value (2.7 x 10(-4) emu/mol) obtained from the experimental data.

Time-resolved resonance Raman spectroscopic studies on the triplet excited state of fluoranil

Perfluoro substituted organic compounds have attracted attention owing to their unique structure and reactivity induced by the perfluoro effect. Fluoranil, a perfluoro derivative of p-benzoquinone, is the subject of this paper. Although the perfluoro effect in the ground state seems to have been well understood there is no information available about such effects on the excited state. Here, the time-resolved resonance Raman spectra of the triplet excited state of fluoranil are reported along with the Raman excitation profiles (REPs) of the various vibrational modes. The vibrational spectral analyses have been carried out by analogy with the fluoranil ground state, triplet benzoquinone, and triplet chloranil vibrational spectral assignments. Also, the assignments are further supported by the calculated frequencies using ab initio theoretical methods. It is observed that for fluoranil in the triplet excited state, due to the perfluoro effect, the structure is considerably less distorted than benzoquinone and also the electron delocalization in the pi* antibonding orbital is less than that of triplet excited state of benzoquinone.

A determination of the structure of the intramolecular charge transfer state of 4-dimethylaminobenzonitrile (DMABN) by time-resolved resonance Raman spectroscopy

Picosecond time-resolved resonance Raman spectra of the A (intramolecular charge transfer, ICT) state of DMABN, DMABN-d(6) and DMABN-N-15 have been obtained. The isotopic shifts identify the nu (s)(ph-N) mode as a band at 1281 cm(-1). The similar to 96 cm(-1) downshift of this mode from its ground state frequency rules out the electronic coupling PICT model and unequivocally supports the electronic decoupling TICT model. However, our results suggest some pyramidal character of the A state amino conformation.

Quantum spin models with exact dimer ground states

Inspired by the exact solution of the Majumdar-Ghosh model, a family of one-dimensional, translationally invariant spin Hamiltonians is constructed. The exchange coupling in these models is antiferromagnetic, and decreases linearly with the separation between the spins. The coupling becomes identically zero beyond a certain distance. It is rigorously proved that the dimer configuration is an exact, superstable ground-state configuration of all the members of the family on a periodic chain. The ground state is twofold degenerate, and there exists an energy gap above the ground state. The Majumdar-Ghosh Hamiltonian with a twofold degenerate dimer ground state is just the first member of the family. The scheme of construction is generalized to two and three dimensions, and illustrated with the help of some concrete examples. The first member in two dimensions is the Shastry-Sutherland model. Many of these models have exponentially degenerate, exact dimer ground states.

Time-Resolved Resonance Raman Spectroscopic Studies on the Triplet Excited State of Thioxanthone

Thioxanthone has been investigated extensively owing to its unique photochemical and photophysical applications and its solvatochromic behavior. Here, we report the time-resolved resonance Raman studies on the structure of the lowest triplet excited state of thioxanthone in carbon tetrachloride. In addition, FT-IR and FT-Raman techniques have been used to study the vibrational structure in the ground state. To corroborate the experimental findings, density functional theory calculations have been carried out. Isotopic calculations and normal coordinate analysis have been used to help in assigning the observed bands to Raman vibrational modes. Structural information derived from this study is expected to help in better understanding the triplet state photochemistry of thioxanthone.

Ab initio, DFT and transition state theory calculations on 1,2-HF, HCI and CIF elimination reactions from CH2F-CH2Cl

This paper reports ab intio, DFT and transition state theory (TST) calculations on HF, HCI and CIF elimination reactions from CH2Cl-CH2F molecule. Both the ground state and the transition state for HX elimination reactions have been optimized at HF, MP2 and DFT calculations with 6-31G*, 6-31G** and 6-311++G** basis sets. In addition, CCSD(T) single point calculations were carried out with MP2/6-311++G** optimized geometry for more accurate determination of the energies of the minima and transition state, compared to the other methods employed here. Classical barriers are converted to Arrhenius activation energy by TST calculations for comparisons with experimental results. The pre-exponential factors, A, calculated at all levels of theory are significantly larger than the experimental values. For activation energy, E-a DFT gives good results for HF elimination, within 4-8 W mol(-1) from experimental values. None of the methods employed, including CCSD(T), give comparable results for HCI elimination reactions. However, rate constants calculated by CCSD(T) method are in very good agreement with experiment for HCI elimination and they are in reasonable agreement for HF elimination reactions. Due to the strong correlation between A and E., the rate constants could be fit to a lower A and E-a (as given by experimental fitting, corresponding to a tight TS) or to larger A and E-a (as given by high level ab initio calculations, corresponding to a loose TS). The barrier for CIF elimination is determined to be 607 U mol(-1) at HF level and it is unlikely to be important for CH2FCH2Cl. Results for other CH2X-CH2Y (X,Y = F/Cl) are included for comparison.

Insulating State and Breakdown of Fermi Liquid Description in Molecular-Scale Single-Crystalline Wires of Gold

Electrical transport measurements on ultrathin single-crystalline Au nanowires, synthesized via a wet chemical route, show an unexpected insulating behavior. The linear response electrical resistance exhibits a power-law dependence on temperature. In addition, the variation of current over a wide range of temperature and voltage obeys a universal scaling relation that provides compelling evidence for a non-Fermi liquid behavior. Our results demonstrate that the quantum ground state In ultrathin nanowires of simple metallic systems can be radically different from their bulk counterparts and can be described In terms of a Tomonaga-Luttinger liquid (TLL), in the presence of remarkably strong electron-electron interactions.

Evolution of ferromagnetism from a frustrated state in LixNi(2-x)O2 (0.67 < x < 0.98)

Two-dimensional triangular-lattice antiferromagnetic systems continue to be an interesting area in condensed matter physics and LiNiO2 is one such among them. Here we present a detailed experimental magnetic study of the quasi-stoichiometric LixNi2-xO2 system (0.67ground states-namely spin glass, cluster glass, re-entrant spin glass and ferromagnetic. This study deals with the magnetic properties of these four distinct ground states. The spin glass state is evidenced by the frequency-dependent peak shift as well as the time-dependent slow dynamics (magnetic relaxation, magnetic memory effect etc). By tuning the Li deficiency in a controlled manner, an increase in the ordering temperature is observed. Most strikingly, with the Li deficiency the nature of the magnetic ground state is changed from spin glass to ferromagnetic, with two intermediate states-namely cluster glass and re-entrant spin glass. The critical behaviour of the re-entrant spin glass is also studied here. The critical exponents (beta, gamma and delta) are extracted from the modified Arrot plot, Kouvel-Fisher method, and critical isotherm analysis. The critical exponents match with the long-range mean-field model. The values of the critical exponents are confirmed by the Widom scaling law: delta = 1 + gamma beta(-1). Furthermore, the universality class of the scaling relations is verified, where the scaled m and scaled h collapse into two branches. Finally, based on our observations, a phase diagram is constructed.

Origin of the Spin-Orbital Liquid State in a Nearly J=0 Iridate Ba3ZnIr2O9

We show using detailed magnetic and thermodynamic studies and theoretical calculations that the ground state of Ba3ZnIr2O9 is a realization of a novel spin-orbital liquid state. Our results reveal that Ba3ZnIr2O9 with Ir5+ (5d(4)) ions and strong spin-orbit coupling (SOC) arrives very close to the elusive J = 0 state but each Ir ion still possesses a weak moment. Ab initio density functional calculations indicate that this moment is developed due to superexchange, mediated by a strong intradimer hopping mechanism. While the Ir spins within the structural Ir2O9 dimer are expected to form a spin-orbit singlet state (SOS) with no resultant moment, substantial frustration arising from interdimer exchange interactions induce quantum fluctuations in these possible SOS states favoring a spin-orbital liquid phase down to at least 100 mK.

Crystal Coulomb energies: I. Organic donor-acceptor complexes--a review. II. Classical Ewald calculations of the Coulomb binding energy of four donor-acceptor crystals and Wurster's blue perchlorate. III. A rapid-convergence quantum-mechanical formalism for crystal electronic energies

Chapter I

Theories for organic donor-acceptor (DA) complexes in solution and in the solid state are reviewed, and compared with the available experimental data. As shown by McConnell et al. (Proc. Natl. Acad. Sci. U.S., 53, 46-50 (1965)), the DA crystals fall into two classes, the holoionic class with a fully or almost fully ionic ground state, and the nonionic class with little or no ionic character. If the total lattice binding energy 2ε₁ (per DA pair) gained in ionizing a DA lattice exceeds the cost 2ε_o of ionizing each DA pair, ε₁ + ε_o less than 0, then the lattice is holoionic. The charge-transfer (CT) band in crystals and in solution can be explained, following Mulliken, by a second-order mixing of states, or by any theory that makes the CT transition strongly allowed, and yet due to a small change in the ground state of the non-interacting components D and A (or D⁺ and A^-). The magnetic properties of the DA crystals are discussed.

Chapter II

A computer program, EWALD, was written to calculate by the Ewald fast-convergence method the crystal Coulomb binding energy E_C due to classical monopole-monopole interactions for crystals of any symmetry. The precision of E_C values obtained is high: the uncertainties, estimated by the effect on E_C of changing the Ewald convergence parameter η, ranged from ± 0.00002 eV to ± 0.01 eV in the worst case. The charge distribution for organic ions was idealized as fractional point charges localized at the crystallographic atomic positions: these charges were chosen from available theoretical and experimental estimates. The uncertainty in E_C due to different charge distribution models is typically ± 0.1 eV (± 3%): thus, even the simple Hückel model can give decent results.

E_C for Wurster's Blue Perchl orate is -4.1 eV/molecule: the crystal is stable under the binding provided by direct Coulomb interactions. E_C for N-Methylphenazinium Tetracyanoquino- dimethanide is 0.1 eV: exchange Coulomb interactions, which cannot be estimated classically, must provide the necessary binding.

EWALD was also used to test the McConnell classification of DA crystals. For the holoionic (1:1)-(N,N,N',N'-Tetramethyl-para- phenylenediamine: 7,7,8,8-Tetracyanoquinodimethan) E_C = -4.0 eV while 2ε_o = 4.6₅ eV: clearly, exchange forces must provide the balance. For the holoionic (1:1)-(N,N,N',N'-Tetramethyl-para- phenylenediamine:para-Chloranil) E_C = -4.4 eV, while 2ε_o = 5.0 eV: again EC falls short of 2ε₁. As a Gedankenexperiment, two nonionic crystals were assumed to be ionized: for (1:1)-(Hexamethyl- benzene:para-Chloranil) E_C = -4.5 eV, 2ε_o = 6.6 eV; for (1:1)- (Napthalene:Tetracyanoethylene) E_C = -4.3 eV, 2ε_o = 6.5 eV. Thus, exchange energies in these nonionic crystals must not exceed 1 eV.

Chapter III

A rapid-convergence quantum-mechanical formalism is derived to calculate the electronic energy of an arbitrary molecular (or molecular-ion) crystal: this provides estimates of crystal binding energies which include the exchange Coulomb inter- actions. Previously obtained LCAO-MO wavefunctions for the isolated molecule(s) ("unit cell spin-orbitals") provide the starting-point. Bloch's theorem is used to construct "crystal spin-orbitals". Overlap between the unit cell orbitals localized in different unit cells is neglected, or is eliminated by Löwdin orthogonalization. Then simple formulas for the total kinetic energy Q^(XT)_λ, nuclear attraction [λ/λ]^XT, direct Coulomb [λλ/λ'λ']^XT and exchange Coulomb [λλ'/λ'λ]^XT integrals are obtained, and direct-space brute-force expansions in atomic wavefunctions are given. Fourier series are obtained for [λ/λ]^XT, [λλ/λ'λ']^XT, and [λλ/λ'λ]^XT with the help of the convolution theorem; the Fourier coefficients require the evaluation of Silverstone's two-center Fourier transform integrals. If the short-range interactions are calculated by brute-force integrations in direct space, and the long-range effects are summed in Fourier space, then rapid convergence is possible for [λ/λ]^XT, [λλ/λ'λ']^XT and [λλ'/λ'λ]^XT. This is achieved, as in the Ewald method, by modifying each atomic wavefunction by a "Gaussian convergence acceleration factor", and evaluating separately in direct and in Fourier space appropriate portions of [λ/λ]^XT, etc., where some of the portions contain the Gaussian factor.

Effect of inter-level relaxation and cavity length on double-state lasing performance of quantum dot lasers

Double-state lasing phenomena are easily observed in self-assembled quantum dot (QD) lasers. The effect of inter-level relaxation rate and cavity length on the double-state lasing performance of QD lasers is investigated on the basis of a rate equation model. Calculated results show that, for a certain cavity length, the ground state (GS) lasing threshold current increases almost linearly with the inter-level relaxation lifetime. However, as the relaxation rate becomes slower, the ratio of excited state (ES) lasing threshold current over the GS one decreases, showing an evident exponential behavior. A relatively feasible method to estimate the inter-level relaxation lifetime, which is difficult to measure directly, is provided. In addition, fast inter-level relaxation is favorable for the GS single-mode lasing, and leads to lower wetting layer (WL) carrier occupation probability and higher QD GS capture efficiency and external differential quantum efficiency. Besides, the double-state lasing effect strongly depends on the cavity length. (c) 2007 Elsevier B.V. All rights reserved.

Delay of the excited state lasing of 1310 nm InAs/GaAs quantum dot lasers by facet coating

In this letter, we present a facet coating design to delay the excited state (ES) lasing for 1310 nm InAs/GaAs quantum dot lasers. The key point of our design is to ensure that the mirror loss of ES is larger than that of the ground state by decreasing the reflectivity of the ES. In the facet coating design, the central wavelength is at 1480 nm, and the high- and low-index materials are Ta2O5 and SiO2, respectively. Compared with the traditional Si/SiO2 facet coating with a central wavelength of 1310 nm, we have found that with the optimal design the turning temperature of the ES lasing has been delayed from 90 to 100 degrees C for the laser diodes with cavity length of 1.2 mm. Furthermore, the characteristic temperature (T-0) of the laser diodes is also improved.